A stereoselective nickel-catalyzed direct borylation of enantioenriched secondary benzyl pivalates is described. This methodology is characterized by an intriguing cooperativity of simple nickel and copper salts to promote the targeted C–B bond formation under mild reaction conditions. Unlike classical SN2-type processes, this protocol occurs with a neat retention of configuration, resulting in synthetically versatile benzyl boronic esters with excellent stereochemical fidelity.
